This invention relates to organosilyl peroxide compounds which are stable in aqueous systems and are used for bleaching and cleaning applications. More particularly, this invention is concerned with the stability of bis(organosilyl)peroxides when formulated in aqueous and non-aqueous delivery systems. The liquid detergents containing the bleaching agent compositions of this invention exhibit excellent bleaching performance and stain removal properties on fabrics at typical low wash temperatures.
Peroxygen bleaching agents, such as hydrogen peroxide, or precursors to hydrogen peroxide such as sodium perborate and sodium percarbonate, are commonly used as bleaching agents in heavy duty granular detergents for laundry application. Attempts have been made in the past to incorporate peroxy bleaching agents in aqueous and non-aqueous liquid detergents for a stable composition and there has always been a lack of stability of peroxy bleaching agent due to its high solubility in aqueous mediums and the decomposition of unstable hydrogen peroxide. Thus, there is no liquid detergent containing bleach commercially available which has an acceptable degree of chemical stability.
Heavy duty liquid detergent compositions (HDL""s) commercially available at present typically comprise organic surfactants, enzymes and perfumes. These components are generally incompatible with peroxygen bleaches. Therefore, no peroxygen bleach containing liquid detergent compositions are commercially available which have long term storage stability.
The preparation of alkyl and aryl silicon peroxide and their uses in washing compositions have been disclosed. For example, in PCT Patent Publication No. WO9714701 is disclosed the preparation of alkyl and aryl silicon peroxides by the reaction of alkoxy or aryloxysilane with H2O2, more specifically tetraalkoxy and tetraaryloxy silane with H2O2 and the use of these silicon peroxides as bleaches.
In European Patent Publication No. 0812907 is disclosed the use of hydroperoxides such as organomineral hydroperoxides including (CH3)3SiOOH, (C6H5)2CH3SiOOH, (C6H5)3SiOOH and (n-C6H13)3SiOOH in a bleaching composition. EP""907 also discloses a process of bleaching fabrics, starting from a liquid composition comprising a hydroperoxide, and discloses that improved fabric safety in terms of loss of tensile strength in the fabrics is obtained by using the hydroperoxides which generate free radicals of lower reactivity.
It has been surprisingly found that the stable aqueous liquid bleach containing detergents can be obtained by using bis(organosilyl)peroxide as a source of active oxygen. The bis(organosilyl)peroxide containing aqueous emulsions and solutions are stable over a wide range of pH and showed a little or no loss of peroxy content when stored for six months at 25xc2x0 C.
This invention relates to a stable liquid bleaching agent composition comprising a bis(organosilyl)peroxide, at least one surfactant selected from the group consisting of at least one nonionic surfactant, at least one anionic surfactant, and a mixture of at least one nonionic surfactant and at least one anionic surfactant, and water.
This invention further relates to a stable liquid bleaching agent composition comprising a bis(organosilyl)peroxide and at least one water soluble alcohol.
It is an object of this invention to produce stable liquid bleaching agent compositions which are stable in solutions and emulsions over a wide range of pH and show a little or no loss of peroxy content when stored for long periods of time.
It is another object of this invention to produce bleaching agent compositions which are useful in laundry detergents.
It is another object of this invention to produce a bleaching agent composition which when added to a laundry detergent, provides the laundry detergent with excellent stain removal at low wash temperatures.
This invention relates to a stable liquid bleaching agent composition comprising: (A) a bis(organosilyl)peroxide having its formula selected from the group consisting of 
xe2x80x83(iii) a mixture of (i) and (ii)
wherein each R1 and each R2 is independently selected from the group consisting of hydrogen, alkyl groups, cycloalkyl groups, aryl groups, alkenyl groups, polyoxyethylene groups, polyoxypropylene groups, and polyoxyethylene-polyoxypropylene groups, or R1 and R2 together form a silicon-containing heterocyclic ring, (B) at least one surfactant selected from the group consisting of at least one nonionic surfactant, at least one anionic surfactant, and a mixture of at least one nonionic surfactant and at least one anionic surfactant, and (C) water.
The alkyl groups of R1 and R2 are exemplified by methyl, ethyl, propyl, butyl, tert-butyl, hexyl, 2-ethylhexyl, n-octyl, decyl, dodecyl, and n-octadecyl, the aryl groups are exemplified by phenyl, tolyl, and xylyl, the cycloalkyl groups are exemplified by cyclopentyl and cyclohexyl, and the alkenyl groups are exemplified by vinyl, allyl, propenyl, butenyl, and hexenyl.
The polyoxyethylene groups are exemplified by groups having the formula xe2x80x94R3(OC2H4)aOR4 wherein R3 is a divalent hydrocarbon group having from 1 to 20 carbon atoms, R4 is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group, and a has an average value from 1 to 150.
The group R3 is a divalent hydrocarbon group having from 1 to 20 carbon atoms which is exemplified by alkylene groups exemplified by methylene, ethylene, trimethylene, tetramethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene, decamethylene, dodecamethylene, and octadecamethylene, and cycloalkylene radicals such as cyclohexylene, arylene radicals such as phenylene, combinations of divalent hydrocarbon radicals such as benzylene (xe2x80x94C6H4CH2xe2x80x94), and oxygen containing groups such as xe2x80x94CH2OCH2xe2x80x94, xe2x80x94CH2CH2CH2OCH2xe2x80x94, xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94COOCH2CH2OOCxe2x80x94, xe2x80x94CH2CH2OCH(CH3)CH2xe2x80x94, and xe2x80x94CH2OCH2CH2OCH2CH2xe2x80x94. Preferred alkylene groups have from 2 to 8 carbon atoms.
The group R4 can be a hydrogen atom, an alkyl group, an aryl group, or an acyl group. The alkyl groups are exemplified by methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl. The aryl groups are exemplified by phenyl, tolyl, and xylyl. The acyl group can have from 1 to 20 carbon atoms and include groups such as acetyl, propionyl, butyryl, isobutyryl, lauroyl, myristoyl, and stearoyl 3-carboxypentadecanoyl. Preferably the acyl group is a group having the formula xe2x80x94OCR5 wherein R5 denotes a monovalent hydrocarbon group. The monovalent hydrocarbon groups of R5 are preferably lower alkyl groups such as methyl, ethyl, or butyl. Preferably a has a value of 1 to 36.
The polyoxypropylene groups are exemplified by groups having the formula xe2x80x94R3(OC3H6)bOR4 wherein R3 is a divalent hydrocarbon group having from 1 to 20 carbon atoms, R4 is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group, and b has an average value from 1 to 150. The groups R3 and R4 are as defined above, including preferred embodiments thereof. Preferably b has a value of 1 to 36.
The polyoxyethylene-polyoxypropylene groups are exemplified by a group having the formula xe2x80x94R3(OC2H4)a(OC3H6)bOR4 wherein R3 is a divalent hydrocarbon group having from 1 to 20 carbon atoms, R4 is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group, and a and b have an average value from 1 to 150. The groups R3 and R4 are as defined above, including preferred embodiments thereof. Preferably a and b have a value of 1 to 36.
The groups R1 and R2 together can form a silicon-containing heterocyclic ring, in such a case, Component (A) is exemplified by bis(cyclotetramethylenesilyl)peroxide.
Each R1 and R2 can be the same or different, as desired. It is preferred that each R1 and each R2 is independently selected from the group consisting of methyl and phenyl, and it is highly preferred that each R1 and R2 is methyl or that each R1 and R2 is phenyl. It is especially preferred that Component (A) is selected from the group consisting of bis(trimethylsilyl)peroxide and bis(triphenylsilyl)peroxide.
Methods of preparing Component (A) have been described in the art, for example by Pike et al., Chemistry and Industry, Sep. 28, 1957, p. 1294, in Chemical Abstract Vol. 54, 1958, p.4471, by Hahn et al., Organosiliciumperoxyde als Initiatoren, 1956, by Berry in U.S. Pat. No. 2,692,887, by Ricci et al., Synthesis 1986, 633, by Cookson et al., Organomet. Chem. 1975, 99 C31, by Dembech, et al., Org. Synth. 74 (1997) p 84-90, by Jackson, W. P., Synlett, 1990, 536, by Tanatar, Russian Chem. Soc., 1906, 40, 376, by Wannagat, Z. Anorg. Allgem. Chem., 1963, 321, 208, by Babin, et al., Synthetic Communications, 22(19), 2849-2852 (1992), by Girsewald, Chem. Ber., 1921, 54, 492, in U.S. Pat. No. 4,161,485, and in U.S. Pat. No. 3,843,703.
Component (A), the bis(organosilyl)peroxide, is generally present in an amount from 0.5 to 90 weight percent (wt %), said wt % being based on the total weight of the stable liquid bleaching agent composition.
Component (B) is at least one surfactant selected from the group consisting of at least one nonionic surfactant, at least one anionic surfactant, and a mixture of at least one nonionic surfactant and at least one anionic surfactant. Examples of suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, polyoxyalkylene glycol modified polysiloxane surfactants, or mixtures thereof.
Examples of suitable anionic surfactants include alkali metal alkyl sulfonates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters such as sodium oleylisethianate, amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride, sulfonated products of fatty acids nitriles such as palmitonitrile sulfonate, sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulfates such as ammonium lauryl sulfate or triethanol amine lauryl sulfate, ether sulfates having alkyl groups of 8 or more carbon atoms such as sodium lauryl ether sulfate or sodium alkyl aryl ether sulfates, alkylarylsulfonates having 1 or more alkyl groups of 8 or more carbon atoms, alkylbenzenesulfonic acids which are exemplified by hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, and myristylbenzenesulfonic acid, salts of alkylbenzenesulfonic acids, sulfuric esters of polyoxyethylene alkyl ether including CH3(CH2)6CH2O(C2H4O)2SO3H, CH3(CH2)7CH2O(C2H4O)3.5SO3H, CH3(CH2)8CH2O(C2H4O)8SO3H, CH3(CH2)19CH2O(C2H4O)4SO3H, and CH3(CH2)10CH2O(C2H4O)6SO3H, sodium salts, potassium salts, amine salts of alkylnaphthylsulfonic acid, and mixtures thereof. Component (B) can also be a mixture of the nonionic surfactants and anionic surfactants described hereinabove.
Component (B), the surfactant, is generally present in an amount from 1 to 85 wt %, and preferably from 2 to 55 wt % said wt % being based on the total weight of the stable liquid bleaching agent composition.
Water (C) forms the remainder of the compositions of this invention and is generally present at a level of from 5 to 85 wt %, preferably from 10 to 65 wt %, said wt % being based on the total weight of the stable liquid bleaching agent composition.
This invention further relates to a stable liquid bleaching agent composition comprising: (A) a bis(organosilyl)peroxide having its formula selected from the group consisting of 
xe2x80x83(iii) a mixture of (i) and (ii)
wherein each R1 and R2 is independently selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, alkenyl groups, polyoxyethylene groups, polyoxypropylene groups, and polyoxyethylene-polyoxypropylene groups, or R1 and R2 together form a silicon-containing heterocyclic ring, and (Bxe2x80x2) at least one water soluble alcohol.
In the above formula, each R1 and each R2 are as described above including preferred embodiments thereof. It is preferred that each R1 and R2 is independently selected from the group consisting of methyl and phenyl, and it is highly preferred that each R1 and R2 is methyl or that each R1 and R2 is phenyl. It is especially preferred that Component (Axe2x80x2) is selected from the group consisting of bis(trimethylsilyl)peroxide and bis(triphenylsilyl)peroxide.
Component (Axe2x80x2), the bis(organosilyl)peroxide, is generally present in an amount from 0.5 to 90 weight percent (wt %), said wt % being based on the total weight of the stable liquid bleaching agent composition.
Component (Bxe2x80x2), is at least one water soluble alcohol, and is exemplified by monohydric and polyhydric alcohols which are liquid at ambient temperature. These alcohols are preferably selected from the group consisting of polyhydric alcohols having from 2 to 3 hydroxyl groups and from 2 to 6 carbon atoms, polymeric polyoxyalkylene alcohols having a molecular weight of from 100 to 4,000, and monoethers and polyethers thereof having at least one free hydroxyl group and an alkyl group having from 1 to 4 carbon atoms. Thus Component (Bxe2x80x2) is exemplified by ethanol, 1,3 propane diol, polyethylene glycols, polypropylene glycols, glycerols, block copolymers of ethylene oxide and propylene oxide, polyoxyethylene glycols having a molecular weight of from 100 to 400, polyoxypropylene glycols having a molecular weight of from 100 to 4,000, polyoxybutylene glycols having a molecular weight of from 100 to 4,000, and mixtures thereof.
Component (Bxe2x80x2), the water soluble alcohol, is generally present in an amount from 5 to 95 wt %, and preferably from 10 to 65 wt % said wt % being based on the total weight of the stable liquid bleaching agent composition.
The stable liquid bleaching agent compositions of this invention are stable in solutions and emulsions over a wide range of pH and show a little or no loss of peroxy content when stored for six months at 25xc2x0 C. The bleaching agent compositions of this invention which contain bis(organosilyl)peroxide are usefull in liquid laundry detergents. The silylperoxides are stable in aqueous emulsions and in solutions as evident from consistent percent active oxygen in the formulation over a long period of time. In the present invention, the silylperoxide compounds do not require a bleach activator or catalyst to promote the oxidation rate. Detergent compositions containing the liquid bleaching agent composition of this invention provide excellent stain removal at low wash temperatures.